Session #6 Batteries
Edison at his West Orange lab with an electric car powered by Edison batteries, 1910
9/29/04 - DPH
History of Battery Development 1600 Gilbert (England) Establishment electrochemistry study 1791 Galvani (Italy) Discovery of ‘animal electricity’ 1800 Volta (Italy) Invention of the voltaic cell 1802 Cruickshank (England) First electric battery capable of mass production 1820 Ampère (France) Electricity through magnetism 1833 Faraday (England) Announcement of Faraday’s Law 1836 Daniell (England) Invention of the Daniell cell 1859 Planté (France) Invention of the lead acid battery 1868 Leclanché (France) Invention of the Leclanché cell 1888 Gassner (USA) Completion of the dry cell 1899 Jungner (Sweden) Invention of the nickel-cadmium battery 1901 Edison (USA) Invention of the nickel-iron battery 1932 Shlecht & Ackermann (Germany) Invention of the sintered pole plate 1947 Neumann (France) Successfully sealing the nickel-cadmium battery 1960 Union Carbide (USA) Development of primary alkaline battery 1970 Development of valve regulated lead acid battery 1990 Commercialization nickel-metal hydride battery 1992 Kordesch (Canada) Commercialization reusable alkaline battery 1999 Commercialization lithium-ion polymer
The nominal voltage of this and the preceding type of cell is 1.6 Ah). They are capable of delivering high intermittent currents and are less prone to electrolyte leakage when exhausted. button-sized cells in equipment where current drains tend to be low . the chief advantage of this type of cell is its ability to function adequately over a large range of temperature. They have poor low-temperature capability and low capacity. such as the RMI2R in an AA (AM3.35) of this type of cell is less than alkaline manganese or silver types and this may be a critical factor in limiting its use. The electrolyte is a potassium hydroxide gel and manganese dioxide acts as the anode. This has a nominal capacity of 3. The discharge characteristic means that a stable voltage is available for most of the cell's service life. MN1500. The shelf life of the cell (in unused condition) is at least 3 years and the discharge curve has a much less pronounced slope than the carbon-zinc type.
.such as light meters or some types of pH meter. Mallory produce some large versions of this type of battery.Types of Primary (Disposable) Batteries
Carbon/zinc batteries — Lecianchd cells with a gelled electrolyte. but the discharge curve is quite steep once the cell starts to become exhausted. Mercury-zinc batteries — These are commonly referred to as 'Mallory' cells and are most commonly met with as small. LR6) size.55. The ammonium chloride electrolyte is mildly corrosive and can cause damage to equipment if exhausted batteries are left in place. Apart from its ability to deliver high currents (the cell chemistry can produce up to 2 A per cell at 2oC). A battery will be exhausted if it delivers less than 1 volt when on load. They have a discharge curve with a pronounced slope and change in voltage with time. First mass produced battery.but costs several times as much. Alkaline-manganese batteries — This type of cell has up to 4 times the energy content of the equivalent size of carbonlzinc. The voltage (1. .9 Ah which is more than double that of the same size alkalinemanganese type (1.
17 . In common with mercury batteries.35 volts of similar-sized mercury types. usually buttonsized. such as memory or clock backup in data loggers. At higher discharge currents. The discharge characteristic is remarkably level for most of the service life of the cell and the voltage is stable over a wide range of moderate to low discharge currents. The lithium thionyl chloride type has a very high energy density and 'is usually employed for low to medium current drain applications. which offer a slightly higher current density and longer service life compared with the previous type of cell. They are often referred to as 'coin' cells because of their appearance and they have similar storage characteristics to the previous type. The capacity of this type of cell is approximately 0. These batteries have a shelf life in excess of 10 years and are rated for operation over a similar period at low levels of discharge current (< 0. The output voltage is stable over a wide range of moderate to low discharge currents and the capacity of the AA size is approximately 1.25 Ah.5 volt types.6 Ah. Lithium batteries — Recent developments in battery technology have lead to the availability of primary cells with outputs in excess of 3 volts and extended temperature tolerance. They are used where their somewhat higher voltage is an advantage compared with the 1. 5-10%/month afterwards)
.0. the output voltage remains constant for most of the battery's life.5 mA).
(Self Discharge: 5% loss in first 24hrs.Types of Primary (Disposable) Batteries (cont’d)
Silver-zinc batteries — These are 1. the capacity appears to be slightly superior to a physically similar-sized alkaline-manganese type. such as memory or clock backup in microprocessor-controlled equipment. The lithium CFX type is intended for low current drain applications.
(Self Discharge: 15% loss in first 24hrs. Main applications are mobile phones. biomedical equipment. high discharge rate and economical price are important. Applications include mobile phones and laptop computers. NiMH contains no toxic metals. (2.Types of Secondary (Rechargeable) Batteries
Nickel Cadmium (NiCd) — mature and well understood but relatively low in energy density. Main applications are two-way radios. emergency lighting and UPS systems. wheelchairs. The NiCd is used where long life. 20-30%/month afterwards)
Lead Acid — most economical for larger power applications where weight is of little concern. This chemistry is similar to the Li-ion in terms of energy density. (1.5V/cell)
. Applications include notebook computers and cellular phones. 2-5%/month
Lithium Ion Polymer (Li-ion polymer) — a potentially lower cost version of the Li-ion.6V/cell) (Self Discharge: 5% loss in first 24hrs.6V/cell) Reusable Alkaline — replaces disposable household batteries. The NiCd contains toxic metals and is not environmentally friendly. The lead acid battery is the preferred choice for hospital equipment. (1. making this battery ideal for portable entertainment devices and flashlights. (1. It enables very slim geometry and allows simplified packaging. The Li-ion is more expensive than other systems and must follow strict guidelines to assure safety. professional video cameras and power tools. 10%/month afterwards)
Nickel-Metal Hydride (NiMH) — has a higher energy density compared to the NiCd at the expense of reduced cycle life. (3.2V/cell)
(Self Discharge: 10% loss in first 24hrs. suitable for low-power applications. Its limited cycle life is compensated by low self-discharge. Li-ion is used where high-energy density and light weight is of prime importance.2V/cell) (Self Discharge: 5%/month) Lithium Ion (Li-ion) — fastest growing battery system. (3.
= OHV vs SHE 0 1.
half-reaction H2 = 2 H+ + 2 eH+ + 1/2 O2 + 2 e. An example is the H2 / O2 fuel cell. which are combined to form water.Fuel Cells: A battery where reactants are supplied to the cell from an external source. in which these gases react (in separate half-reactions at separate electrodes) to form protons and hydroxide.2
Battery Lifecycle Cost
Battery Lifecycle Cost
The overall cell reaction is: 2 NiOOH + 2H2O + Cd = 2 Ni(OH)2 + Cd(OH)2
Li + MnO2 —> LiMnO2
These batteries contain a Ni(OH)2 cathode. The half-cell reactions are: Pb + SO42.= Mn2O3 + 2 OH-
First commercialized over a century ago by Plante.= PbSO42.(sol) + 2 ePbO2 + 4 H+ + 2 e. Zn + 2 OH.= Zn(OH)2 + 2 e2 MnO2 + H2O + 2 e.+ SO42. they are primarily used as car batteries. a high grade MnO2 cathode and a KOH aqueous electrolyte. Pb anode. and sulfuric acid electrolyte. The cells are constructed from a PbO2 cathode.Battery Chemistry
Anode (negative terminal) Oxidation reaction Cathode (positive terminal) Reduction reaction
These batteries use a high-surface-area Zn powder anode. Cd anode and aqueous KOH electrolyte.= PbSO42.
The positive plate is sintered and filled with nickel hydroxide.
.Cross-section of a classic NiCd cell. A separator moistened with electrolyte isolates the two plates. The negative plate is coated with cadmium active material.
The negative and positive plates are rolled together in a metal cylinder.
The prismatic cell improves space utilization and allows more flexibility in pack design. This cell construction is less cost effective than the cylindrical equivalent and provides a slightly lower energy density.
.Cross-section of a prismatic cell.
The button cell offers small size and ease of stacking but does not allow fast charging. Coin cells. are normally lithium-based and are non-rechargeable. which are similar in appearance.The button cell.
Ohmic. inductive and capacitive resistance in batteries. Ro = ohmic resistance Qc = constant phase loop (type of capacitance) L = inductor Zw = Warburg impedance (particle movement within the electrolyte) Rt = transfer resistance
• • • • •
Effects of temperature on NiCd charge acceptance. Charge acceptance is much reduced at higher temperatures. NiMH cells follow a similar pattern.
pressure and temperature characteristics are similar in a NiMH cell
. These cell voltage.Charge characteristics of a NiCd cell.
The same battery discharged at 0.5C would be a two-hour. Most portable batteries. the same battery delivers 2000mA for 30 minutes. a battery rated at 1000mAh provides 1000mA for one hour if discharged at 1C rate. a 0.The charge and discharge current of a battery is measured in C-rate. For example.5C provides 500mA for two hours. and a 0. 1C is often referred to as a one-hour discharge. A discharge of 1C draws a current equal to the rated capacity. are rated at 1C. At 2C.1C a 10 hour discharge
. with the exception of the lead acid.
which means that the lost cell capacity which results from a severe overcharge is not recoverable. the cell that goes down to zero volts first will continue to have current forced through it by the other cells. Both Ni-Cd and Ni-MH cells have internal vents which will open to allow gas to escape and prevent explosion of the cell. Avoiding abusive high-current overcharge can only be ensured with a well-designed charging system that responds to the signal the battery gives when fully charged. Cell polarity reversal is a potential problem with any series-connected string of cells: as the battery is discharged. It is never wise to rely on the cell's vent as a failsafe. it is essential to terminate charge when the cell is full. because they often corrode over time and can not be assumed to be absolutely reliable. while a Ni-MH cell will vent hydrogen. the voltage across the fully-discharged cell is reversed. A cell that has current forced through it with a reverse voltage across it will heat up very quickly and vent gas in a similar mode to that described for the sustained overcharge. If this is not done. the gas released is oxygen.Reliability Battery makers (and common sense) tell us that most of the problems with rechargeable batteries can be traced to misuse: NI-CD and NI-MH: HOW CELLS ARE DAMAGED Sustained high-current overcharge and cell polarity reversal (during discharge) are the main killers of Ni-Cd and Ni-MH batteries: If a high charge rate is used. In the case of Ni-Cd. with the same resultant damage. When this occurs.
. the temperature and pressure within the cell will rise quickly as the charging current is dissipated as heat. The gas that is lost can never be replaced.
with no major problems reported. The annoyance factor of batteries that go dead quickly often prompts users to throw away leaky Ni-Cd batteries. User feedback (so far) on Ni-MH has been good. At present. A leaky Ni-Cd cell will always have a high self-discharge rate and will re-grow internal shorts if left on the shelf without some kind of trickle charge. as there were many failures in the first batteries shipped. However. there are no known problems which appear significant enough to prevent LiIon from successfully penetrating the high-end consumer market.AGE-RELATED FAILURE MODES Ni-Cd: After a period of time. If this happens. Ni-MH: The Ni-MH cell (according to the manufacturers) is not supposed to be prone to developing internal shorts like a Ni-Cd battery.
. the insulator within a Ni-Cd battery often develops holes which allow the cell to grow crystalline "shorts" that provide a conduction path between the positive and negative electrodes of the cell (which basically shorts out the cell). even though they may still be able to give nearly full A-hr capacity during discharge. you may have to blow open this short with a high current pulse before the cell will again accept charge (a process sometimes referred to as "zapping"). the addition of the internal protection circuitry inside the battery (and increased knowledge about the failure modes) has improved this. Li-Ion: The Li-Ion battery got off to a weak start.
an almost 100% restoration (capacity of 8.1Ah). Restored cell.
Crystalline formation on NiCd cell. the crystals are reduced to 3 to 5 microns.5Ah). After pulsed charge. Exercise or recondition are needed if the pulse charge alone is not effective. Cell with crystalline formation. exposing large surface area to the liquid electrolyte for maximum performance. Hexagonal cadmium hydroxide crystals are about 1 micron in cross section. Jagged edges and sharp corners may pierce the separator.0A). The anode is in fresh condition (capacity of 8. Crystals have grown to an enormous 50 to 100 microns in cross section. which can lead to increased self-discharge or electrical short.
. concealing large portions of the active material from the electrolyte (capacity of 6.New NiCd cell.